Coating composition

ABSTRACT

A coating composition comprising an aqueous mixture containing acid-stable particles and one or more fluoroacids. The amount of the acid-stable particles in the coating composition is from 0.005% to 8% by weight on a dry weight basis. The acid-stable particles can be selected from aluminum-modified silica particles, nonaluminum-modified silica particles, and organic particles selected from anionically stabilized polymer dispersion particles. The invention is also directed to a coating on a metal substrate. The coating contains acid-stable particles attached to the metal substrate through a metal-oxide matrix. The metal-oxide matrix comprises a metal selected from titanium, zirconium, silicon, hafnium, boron, aluminum, germanium, or tin.

FIELD OF THE INVENTION

The present invention relates to coating compositions, in particular,coating compositions that can be applied to metal substrates to enhancecorrosion resistance. The invention also relates to coatings resultingfrom the coating compositions.

BACKGROUND OF THE INVENTION

A coating is often applied to metal substrates, especially metalsubstrates that contain iron such as steel, prior to the application ofa protective or decorative coating. The coating minimizes the amount ofcorrosion to the metal substrate, if and when, the metal substrate isexposed to moisture and oxygen. Many of the present coating compositionsare based on metal phosphates, and rely on a chrome-containing rinse.The metal phosphates and chrome rinse solutions produce waste streamsthat are detrimental to the environment. As a result, there is theever-increasing cost associated with their disposal.

Coating compositions can be applied without chrome rinse solutions. Forexample, U.S. Pat. No. 3,966,502 discloses post-treating phosphatedmetals with zirconium-containing rinse solutions. However, thisapplication process is only suitable for use over a limited number ofmetal substrates, and the generation of metal phosphate waste streams isnot alleviated.

U.S. Pat. No. 5,534,082 to Dollman et al. and U.S. Pat. Nos. 5,281,282and 5,356,490 to Dolan et al. describe non-chrome coating compositioncontaining a fluoroacid such as fluorotitanic acid, silica, and awater-soluble polymer such as an acrylic acid polymer and/or a polymerwith hydroxyl functionality. By heating the silica and fluoroacid, thesilica is dissolved, or at least partially dissolved, until the solutionis clear. As a result, the silica particles used in these coatingcompositions are not acid-stable particles. The pH of these compositionsis very acidic, and ranges from 0 to 4, preferably from 0 to 1. Thecoatings compositions enhance the corrosion resistance of steel andgalvanized steel substrates.

U.S. Pat. No. 5,938,861 to Inoue et al. describes forming a coating onmetal substrates, except aluminum. The coating composition includes anoxidative compound such as nitric acid or hydrogen peroxide, silicate orsilicon dioxide particles, and a metal cation, oxymetal anion, orfluorometallate anion of Ti, Zr, Ce, Sr, V, W, and Mo.

EP 1130131A2 to Toshiaki et al. describes a non-chrome coatingcomposition that contains a metallic surface-treating agent,water-dispersible silica, and one or more of a zirconium or titaniumcompound, thiocarbonyl compound, and a water-soluble acrylic resin. Themetallic surface treating agent is selected from a provided list ofsilane coupling agents that are typically used in the coating industryto improve adhesion between the pre-coating and the decorative coating.

U.S. Pat. No. 5,859,106 to Jones et al. describes a non-chrome coatingcomposition that contains a cross-linked polymer system, which includesa copolymer with acrylic and hydroxyl functionality or the reactionproduct of an acrylic polymer and a polymer with hydroxyl functionality.A fluoroacid such as fluorozirconic acid or fluorotitanic acid can beadded to these compositions. U.S. Pat. No. 5,905,105 to Jones et al.describes a non-chrome coating composition that includes the coatingcomposition described in U.S. Pat. No. 5,859,106 with the addition ofdispersed silica and an ammonium carbonate containing a group IVB metal.

There is an interest to develop coating compositions and methods ofapplying such compositions without producing metal phosphate and chromewaste solutions. It is also preferred, that these coating compositionsbe effective in minimizing corrosion in a variety of metal substratesbecause many objects of commercial interest contain more than one typeof metal substrate. For example, the automobile industry often relies onmetal components that contain more than one type of metal substrate. Theuse of a coating composition effective for more than one metal substratewould provide a more streamlined manufacturing process.

SUMMARY OF THE INVENTION

The invention is directed to a coating composition and a process ofmaking the coating composition. The coating composition comprises anaqueous mixture comprising acid-stable particles, and one or morefluoroacids. The invention is also directed to a process of making thecoating compositions.

The invention is also directed to a coating on a metal substrate. Thecoating comprises acid-stable particles attached to the metal substratethrough a metal-oxide matrix. The particles are acid-stable in theacidic, aqueous coating composition. The metal-oxide matrix comprisesone or more metals selected from the group consisting of titanium,zirconium, silicon, hafnium, boron, aluminum, germanium, and tin. Thecoating coverage of the metal substrate is from 5 mg/sq ft to 50 mg/sqft.

BRIEF DESCRIPTION OF THE DRAWING

The invention will be better understood by reference to the DetailedDescription of the Invention when taken together with the attacheddrawing, wherein

FIG. 1 is a plot of coating weights and compositions on CRS panels vs.spray time for coatings provided by a coating composition of theinvention;

FIG. 2 is a plot of coating weights on CRS panels vs. spray time forcoatings provided by other coating compositions of the invention; and

FIG. 3 is yet another a plot of coating weights on CRS panels vs. spraytime for coatings provided by still other coating compositions of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

The coating composition comprises an aqueous mixture comprisingacid-stable particles and one or more fluoroacids. The aqueous mixturecan also contain a product of the acid-stable particles and the one ormore fluoroacids. Particles are acid-stable if the change in viscosityas measured in a test sample, as described herein under the subheading,“Test procedure for acid-stable particles”, is ten seconds or less,preferably five seconds or less. In most cases, test samples thatcorrespond to the acid stable particles of the invention will have achange in viscosity of three seconds or less. In the most preferredembodiments, the acid-stable particles will have a change in viscosityof one second or less. Typically, the lower the change in viscosity themore stable the particles are in acid, that is, in an aqueous solutionwith a pH of 3 to 7.

The term “change in viscosity” used herein reflects the viscositymeasurement made in accordance to the described test procedure. Withrespect to some of the compositions of the invention, theircorresponding test samples can over 96 hours actually decrease inviscosity such that the measured change in viscosity is less than zero.

Alternatively, one of ordinary skill can determine if particles areacid-stable by preparing an acidified test sample containing theparticles as described, and simply observing whether there is anyvisible indication of thickening, precipitation or gelling over about 96hours at room temperature.

Typically, the acid-stable particles of the invention will maintain anegative charge at a pH from about 2 to about 7. In some cases, theacid-stable particles will maintain a negative charge at a pH from about3 to about 6. In still other cases, the acid-stable particles willmaintain a negative charge at a pH from about 3.5 to about 5.

One way to determine whether the acid-stable particles maintain anegative charge is by measuring the Zeta Potential of the particles.This measurement can be carried out using commercially availableinstruments such as a Zetasizer 3000HSA from Malvern Instruments Ltd. Anegative measured voltage indicates the particles are negativelycharged. Exemplary Zeta Potentials for silica-based, acid-stableparticles used in the coating compositions are −5 to −35 mV. ExemplaryZeta Potentials for the organic, polymeric acid-stable particles used inthe coating compositions are −55 to −85 mV.

The coating composition of the invention also contains water. Water isused to dilute the coating composition of the invention, and providesrelatively long-term stability to the composition. For example, acomposition that contains less than about 40% by weight water is morelikely to polymerize or “gel” compared to a coating composition withabout 60% or greater by weight water under identical storage conditions.Although the coating compositions of the invention typically applied tothe substrate will contain about 92% water or greater, it is to beunderstood that a coating composition of the invention also includes aconcentrated formulation composition with 60% to 92% by weight water.The end-user simply dilutes the concentrated formulation with additionalwater to obtain an optimal coating composition concentration for aparticular coating application.

The coating composition of the invention can be provided as aready-to-use coating composition, as a concentrated coating compositionthat is diluted with water prior to use, as a replenishing composition,or as a two component coating system. In a two-component coating systemthe fluoroacid is stored separately from the particles. The fluoroacidand the particles are then mixed prior to use by the end-user.

The concentration of each of the respective components of the coatingcompositions will, of course, be dependent upon whether the coatingcomposition to be used is a replenishing coating composition, aconcentrated coating composition, or a ready-to-use coating composition.A replenishing coating composition can be provided to and used by anend-user to restore an optimal concentration of components of a coatingcomposition to a coating bath as the components are consumed during thecoating of substrates. As a result, a replenishing coating compositionwill necessarily have a higher concentration of acid-stable particles orfluoroacids than the coating composition used to coat the substrate.

The concentration of acid-stable particles in the compositions of theinvention depends on the type of particles used and the relative size,e.g., average diameter, of the particles. The coating compositions willcontain from 0.005% to 8% by weight, 0.006% to 2% by weight, 0.007% to0.5% by weight, or from 0.01% to 0.2% by weight, on a dry weight basisof acid-stable particles.

Acid-stable silica particles can be aluminum-modified silica particles.Aluminum-modified silica particles will have a weight ratio ofSiO₂:Al₂O₃ from about from about 80:1 to about 240;1, and from about120:1 to about 220:1. The concentration of aluminum-modified silicaparticles in the compositions of the invention is from 0.005% to 5% byweight, 0.006% to 1% by weight, 0.007% to 0.5% by weight, or from 0.01%to 0.2% by weiglht, on a dry weight basis of acid-stable particles.

In one embodiment, the acid-stable particles used in a coatingcomposition are silica particles provided as a colloidal suspension fromGrace Davison under the trademark Ludox® TMA, Ludox® AM, Ludox® SK, andLudox® SK-G. These specific types of silica particles are treated withan aluminum compound, believed to be sodium aluminate. For example,Ludox® AM has a weight ratio of SiO₂:Al₂O₃ from about 140:1 to 180:1.Aluminum-modified silica such as Adelite® AT-20A obtained from AsahiDenka can also be used.

The acid-stable particles can be relatively spherical in shape with anaverage diameter from about 2 nm to about 80 run, or from about 2 nm toabout 40 nm, as measured by transmission electron microscopy (TEM). Theparticles can also be rod-shaped with an average length from about 40 nmto about 300 nM, and an average diameter from about 5 nm to about 20 nm.The particles can be provided as a colloidal dispersion, e.g., as amono-dispersion in which the particles have a relatively narrow particlesize distribution. Alternatively, the colloidal dispersion can bepoly-dispersed in which the particles have a relatively broad particlesize distribution.

The silica particles are typically in the form of discrete spheressuspended in an aqueous medium. The medium can also contain a polymer toimprove stability of the colloidal suspension. The polymer can be one ofthe listed polymers provided below. For example, certain commerciallyavailable formulations include a polymer to maintain stability of thedispersion during storage. For example, Ludox® SK and Ludox® SK-G aretwo commercial forms of colloidal silica that contain a polyvinylalcohol polymer.

It is to be understood, that the coating compositions do not require thepresence of a polymer to maintain acid stability of the compositions ata pH from 2 to 7. However, in some applications, a polymer can be addedto the coating compositions to provide even greater acid stability.

As indicated by the comparative coating compositions the use of Ludox®AS, Ludox® HS, and Ludox® TM silica particles do not provide acid-stablecoating compositions, and thus are not acid-stable particles. That isnot to say that these non acid-stable particles cannot be present in thecoating compositions of the invention in relatively small amounts. It isto be understood, that the amount or concentration of non acid-stableparticles that can be present in the coating compositions will dependupon the type of non acid-stable particles, the pH of the composition,the type of fluoroacid used, and the type and concentration ofacid-stable particles in the composition, Of course, one of ordinaryskill would also recognize that one or more different types ofacid-stable silica particles can be combined in a coating composition ofthe invention.

In another embodiment, the acid-stable particles can benonaluminum-modified silica particles. These silica particles aremodified by some process, at times a proprietary process, that is notconsidered by those skilled in the art to be an aluminum modificationprocess. The nonaluminum-modified silica particles are negativelycharged and have a majority of silicon acid sites neutralized, forexample, by sodium or ammonia. Examples of nonaluminum-modified silicaparticles that can be used in the coating compositions include colloidalparticles from Nissan Chemical sold under the trademark Snowtex® O andSnowtex® N. The concentration of nonaluminum-modified silica particlesin the compositions of the invention is from 0.005% to 5% by weight,0.006% to 1% by weight, 0.007% to 0.5% by weight, or from 0.01% to 0.2%by weight, on a dry weight basis of acid-stable particles.

In another embodiment, a selection of organic, polymeric acid-stableparticles can be used in the coating compositions. For example,polymeric particles selected from the group consisting of anionicallystabilized polymer dispersions, such as epoxy-crosslinked particles,epoxy-acrylic hybrid particles, acrylic polymer particles,polyvinylidene chloride particles, and vinyl acrylc/vinyidinechloride/acrylic particles provide acid-stable coating compositions.Three commercially available polymeric particles that can be usedinclude ACC 800 and ACC 901 from Henkel Corp., and Haloflex® 202 fromAvecia, Inc. ACC 901 includes epoxy-crosslinked particles, ACC 800includes polyvinylidene chloride particles. Haloflex® 202 includes vinylacrylic/vinylidine chloride/acrylic particles. The concentration oforganic polymeric particles in the compositions of the invention is from0.01% to 8% by weight, from 0.01% to 5% by weight, and from 0.1% to 3%by weight, on a dry weight basis.

The fluoroacid is an acid fluoride or acid oxyfluoride with an elementselected from the group consisting of Ti, Zr, Hf, Si, Sn, Al, Ge and B.The fluoroacid should be water-soluble or water-dispersible andpreferably comprise at least I fluorine atom and at least one atom of anelement selected from the group consisting of Ti, Zr, Hf, Si, Sn, Al, Geor B. The fluoroacids are sometimes referred to by workers in the fieldas “fluorometallates”,

The fluoroacids can be defined by the following general empiricalformula (I):H_(p)T_(q)F_(r)O_(s)   (I)

wherein: each of q and r represents an integer from 1 to 10; each of pand s represents an integer from 0 to 10; T represents an elementselected from the group consisting of Ti, Zr, Hf, Si, Sn, Al, Ge, and B.Preferred fluoroacids of empirical formula (I) include: T is selectedfrom Ti, Zr, or Si; p is 1 or 2; q is 1; r is 2, 3, 4, 5, or 6; and s is0, 1, or 2.

One or more of the H atoms may be replaced by suitable cations such asammonium, metal, alkaline earth metal or alkali metal cations (e.g., thefluoroacid can be in the form of a salt, provided such salt iswater-soluble or water-dispersible). Examples of suitable fluoroacidsalts include (NH₄)₂SiF₆, MgSiF₆, Na₂SiF₆ and Li₂SiF₆.

The preferred fluoroacids used in the coating compositions of theinvention are selected from the group consisting of fluorotitanic acid(H₂TiF₆), fluorozirconic acid (H₂ZrFe₆), fluorosilicic acid (H₂SiF₆),fluoroboric acid (HBF₄), fluorostannic acid (H₂SnF₆), fluorogermanicacid (H₂GeF₆), fluorohafnic acid (H₂HF₆), fluoroaluminic acid (H₃AlF₆),and salts of each thereof The more preferred fluoroacids arefluorotitanic acid, fluorozirconic acid, fluorosilicic acid, and saltsof each thereof. Some of the salts that can be used include alkali metaland ammonium salts, e.g., Na₂M₆ and (NH₄)₂ MF₆, where M is Ti, Zr, andSi.

The concentration of the one or more fluoroacids in the coatingcompositions of the invention can be relatively quite low. For example,a fluoroacid concentration of about 5 ppm can be used, and still providecorrosion resistant coatings (ppm=parts per million). The concentrationof the one or more fluoroacids in the coating compositions is from about5 ppm (about 0.0005% by weight) to about 10,000 ppm (about 1.0% byweight), from about 5 ppm to about 1000 ppm and from 5 ppm to about 400ppm. The preferred concentrations of the one or more fluoroacids in thecoating compositions is from about 3 ppm to about 3000 ppm, morepreferably from about 10 ppm to about 400 ppm. The final concentration,of course, will depend upon the amount of water used to prepare thecoating compositions of the invention.

The addition of catechol compounds in the coating compositions can beused to provide a visible color indicator that the metal substrate isindeed coated. Without the catechol compound, the resulting coatings canbe, at times, too thin to be visible. The term “catechol compound” isdefined as an organic compound with an aromatic ring system thatincludes at least two hydroxyl groups positioned on adjacent carbonatoms of the aromatic ring system.

The preferred catechol compounds used to prepare the coatingcompositions of the invention are negatively charged or neutral, thatis, have no charge. The negatively charged catechol compounds arecommonly available as metal salts, particularly as alkali or alkalineearth metal salts.

The concentration of catechol compound in the coating compositions ofthe invention can be optimized by those skilled in the art to provide avisible coating. The concentration of the catechol compound will dependon the type of catechol compound used. Also, each catechol compound canbe expected to have a different interaction with each type ofacid-stable particles used in the coating composition. As a result, theoptimal concentration of catechol compound depends upon which type(s) ofacid-stable particles are used in the coating compositions. Lastly,because any excess catechol compound can be removed with a rinse stepfollowing application of the coating composition to a metal substrate,the concentration of the catechol compound can be greater than what isrequired to provide a visibly colored coating.

In one embodiment, the catechol compound is selected from the alizarinseries of compounds. For example, alizarin, alizarin red, alizarinorange, and the salts of each thereof can be used to prepare the coatingcompositions of the invention. One preferred alizarin compound isalizarin red, i.e., 3,4-dihydroxy-9,10-dioxo-2-anthracenesulfonic acidor the salt thereof.

In another embodiment, the catechol compound is selected frompyrocatechol, and conjugated pyrocatechols. The term “conjugatedpyrocatechol” is defined as pyrocatechol with a conjugated ring system.Pyrocatechol sulfonephthalein, i.e., pyrocatechol violet, or the saltsthereof is one preferred conjugated pyrocatechol.

The coating compositions of the invention can also include one or morepolymers. The one or more polymers preferably comprise functional groupsselected from hydroxyl, carboxyl, ester, amide, or combinations thereof.The functional groups on the polymers are believed to serve variousfunctions. First, prior to forming the coatings, the functional groupsprovide a polymer that has a relatively high solubility or miscibilityin water. Second, the frictional groups provide points along the polymerbackbone through which cross-linking between the polymers can occur asthe coating composition cures to form a coating on a metal substrate.Third, the functional groups on the polymer are believed to enhancebinding between the metal substrate and particles in the cured coating.

An exemplary list of the one or more polymers used are selected frompolyvinyl alcohol, polyester, water-soluble polyester derivatives,polyvinylpyrrolidone, polyvinylpyrrolidone-vinyleaprolactam copolymer,polyvinylpyrrolidone-vinylimidazole copolymer and sulfonatedpolystyrene-maleic anhydride copolymer. The most preferred polymers usedinclude polyvinyl alcohol, polyvinylpyrrolidone-vinylcaprolactamcopolymer. Luvitec® and Elvanol® are two commercially available types ofpolymers that can be used to prepare a coating composition of theinvention. Luvitec® is a vinylpyrrolidone-vinylcaprolactam polymeravailable from BASF. Elvanol® is a polyvinyl alcohol polymer availablefrom Dupont.

In the presence of one or more of the above polymers, the fluoroacidscan function as a curing agent as well as a binding agent. It isbelieved that the fluoroacid reacts with the functional groups of thepolymer, and thus can provide a means for the polymer to cross-link. Thecross-linking of the polymer in combination with the fluoroacid providesa cement-like polymer-metal oxide matrix that binds the particles toform a coating on a metal substrate.

A coating composition of the invention is prepared by a processcomprising: providing acid-stable particles and one or more fluoroacids;and mixing the acid-stable particles and the one or more fluoroacids inwater. The amount of acid-stable particles in the coating composition isfrom 0.005 to 8% by weight on a dry weight basis. Preparation of thecoating composition can also include one or more polymers exemplified inthe list above, and mixing the polymer with the other components.

The pH of a coating composition of the invention ranges from about 2 toabout 7, preferably from about 3 to about 6, and more preferably fromabout 3.5 to about 5. The pH of the coating composition can be adjustedusing mineral acids such as hydrofluoric acid, phosphoric acid, and thelike, including mixtures thereof. Alternatively, additional amounts ofthe fluoroacids can be used. Organic acids such as lactic acid, aceticacid, citric acid, sulfamic acid, or mixtures thereof can also be used.

The pH of the coating composition can also be adjusted by adding smallamounts of an alkali material, typically in the form of a metal orammonium hydroxide, carbonate, or bicarbonate. Exemplary inorganic andorganic bases include sodium hydroxide, ammonium hydroxide, ammonia, oramines, e.g., triethanolamine or other alkylamines.

The coating compositions can also include one or more secondary agentsselected from a leveling agent, a wetting agent, an antifoaming agent,and a bonding agent. However, one of ordinary skill would understandthat the use of such agents, and the concentrations at which they areused, must be compatible within the pH range of the coating composition.The addition of too much of a secondary agent could significantlydiminish the acid stability of the compositions.

The coating composition of the invention can be applied to a metalsubstrate to form a corrosion resistant coating. Metal substrates thatcan be passivated (provided with enhanced corrosion resistance) by thecoating compositions of the invention include cold rolled steel,hot-rolled steel, stainless steel, steel coated with zinc metal, zincalloys such as electrogalvanized steel, galvalume, galvanneal, andhot-dipped galvanized steel, aluminum alloys and aluminum plated steelsubstrates. The invention also offers the advantage that componentscontaining more than one type of metal substrate can be passivated in asingle process because of the broad range of metal substrates that canbe passivated by the coating compositions of the invention.

Although not necessary, the metal substrate is usually cleaned to removegrease, dirt, or other extraneous materials by using conventionalcleaning procedures and materials, e.g., mild or strong alkalinecleaners. Examples of alkaline cleaners include Parco® Cleaner ZX-1 andParco® Cleaner 315, both of which are available from Henkel SurfaceTechnologies. The metal substrate is then rinsed with water or anaqueous acidic solution. The metal substrate can also be treated with acommercially available metal phosphate solution, e.g., iron or zincphosphate solutions, prior to contacting the metal substrate with acoating composition of the invention.

A coating composition of the invention is applied to the metalsubstrates in any number of ways known in the art. Two of the mostpreferred methods are spraying and immersion. The thickness andcomposition of the cured coating on the metal substrate depends on anumber of factors including particle size, particle concentration, andexposure time or time in contact with the coating composition.

FIG. 1 is provided to show how the composition of a dried coating on aCRS panel prepared from the coating composition of Example 1 can changewith spray time. As shown, the concentration of silica ( weight ofsilicon and oxygen) ill the coating is relatively independent of spraytime, that is, the amount of silica is relatively constant at about 14to 17 mg/sq ft over a spray time of about 25 to 100 seconds. This wouldbe expected given the proposed monolayer structure of the coating.

FIGS. 2 and 3 depict differences in the thickness coatings over a spraytime of about 25 to 125 seconds for selected coating compositions of theinvention.

In contrast, the amount of titanium and zirconium in the coating isshown to increase linearly with time. The amount of metal in the coatingis from 0.5 mg/sq ft to 6 mg/sq ft. In many instances, the amount ofmetal in the coatings is from 0.5 mg/sq ft to 3 mg/sq ft.

The coatings resulting from the compositions of the invention arerelatively low weight coatings when compared to present coatingtechnologies. The coatings of the invention have a coating weight from 5mg/sq ft to 50 mg/sq ft. In many instances, however, the coatings willhave a coating weight from 8 mg/sq ft to 30 mg/sq ft. In fact, coatingswith a coating weight from 8 mg/sq ft to 20 mg/sq ft are typicallyformed from the coating compositions.

Following treatment of a metal substrate with a coating composition, thecoating composition can be dried in place on the surface of the metalsubstrate. Alternatively, the applied coating composition can be rinsed,preferably with water, to remove excess coating composition, and thendried. The drying can be done at any temperature. Typical convenienttemperatures are from 100° F. to 300° F. The drying conditions selecteddepend upon the customer's preferences, space available, and the type offinish coating used. For example, a powder coating typically requires adry surface prior to application compared to a water-based coating.

The coating comprises acid-stable particles attached to the metalsubstrate through a metal-oxide matrix. In the context of a curedcoating on a metal substrate, the use of the term “acid-stable” particleto describe the particle in the coating refers to particles that provideacid-stable coating compositions defined herein. The metal-oxide matrixcomprises one or more metals selected from the group consisting oftitanium, zirconium, silicon, hafnium, boron, aluminum, germanium, andtin. The metal-oxide matrix preferably comprises one or more metalsselected from titanium, zirconium, and silicon. If a water solublepolymer is present in the coating composition, the metal-oxide matrixcan farther contain a reaction product of the one or more polymers andthe one or more fluoroacids or salts of each thereof. The coating of theinvention can he described as a brick and mortar coating with theparticles represented by the bricks and the metal oxide matrixrepresented by the mortar.

One advantage of the coatings of the invention is that they providecomparable and, in most instances, improved corrosion resistancerelative to present iron phosphate coating technology. Also, thisimprovement in corrosion resistance is achieved with a coating coveragethat is significantly less than present iron phosphate coatings. Forexample, to provide an acceptable degree of corrosion resistance to aCRS panel, iron phosphate coatings are applied at a coverage level fromabout 50 mg/sq ft to 150 mg/sq ft. In contrast, a coating of theinvention can provide a similar degree of corrosion resistance at acoverage level from 8 mg/sq ft to 30 mg/sq ft. In most cases, a coatingof the invention exhibits an acceptable degree of corrosion resistanceat coverage levels from 8 mg/sq ft to 20 mg/sq ft.

Another advantage of the coatings of the invention over iron phosphatecoatings is exhibited through its relatively high flexibility anddurability. In impact tests and bending tests the coatings of theinvention typically maintain their corrosion resistance while the ironphosphate coatings do not. Moreover, these tests were performed withcoatings of the invention at coverage levels of less than 20 mg/sq ft,while the iron phosphate coatings had coverage levels of about 65 mg/sqft.

Additional coatings can then be applied. In most cases, these coatingscan be a primer paint composition or a final paint coating such as afinish coat. One of the many advantages of the coatings of the inventionis that the coatings are compatible with any number of protective paintssuch as Duracron® 200, which is a high solid, acrylic paint from PPGIndustries, and powder paints such as Sunburst® Yellow, which is apolyester powder paint from Morton International. The coatings of theinvention are also compatible with paints that are applied byelectrodeposition.

The invention and its benefits will be better understood with referenceto the following examples. These examples are intended to illustratespecific embodiments within the overall scope of the invention asclaimed, and are not to be understood as limiting the invention in anyway.

1. Test Procedure for Acid-Stable Particles.

Prepare a sodium acetate/acetic acid buffer with a pH of about 5.0 byacidifying the solution with hydrochloric acid. To 20 mL of buffersolution add 20 mL of the selected particle dispersion. As a testsample, the particle dispersion should have a silica concentration ofabout 30 wt %. If the selected particle dispersion has a higher wt %,dilute the dispersion to 30 wt %. Stir the solution for ten minutes.Observe whether the solution remains fluid, that is, whether there isany visible indication of thickening, precipitation or gelling overabout 96 hours at room temperature. An experimental method used toqualitatively define acid-stable particles is to measure the change inviscosity of a test sample above after 84 hours at room temperature.Applicants measure the change in viscosity using a Zahn Cup apparatusfrom Gardner Laboratory Division, Pacific Scientific Co.

The Zahn viscosity cup is a small U-shaped cup suspended from a wire.The cup has an orifice, which is available in various sizes, at itsbase. For example, the #2 Zahn cup used in the acid stability test iscertified to ASTM D4212 with an orifice diameter of 2.69 mm. Theviscosity of a sample is measured by completely submerging the cup intothe test sample. The cup is then completely withdrawn from the sample.The time in seconds from the moment the top of the cup emerges from thesample until a portion of the stream breaks free from the stream fallingthrough the orifice is the measure of the viscosity of the sample.

Following the acid-stability procedure described above, a sodiumacetate/acetic acid buffer with a pH of about 5.0 was prepared. 20 mL ofthe selected particle dispersion was added to 20 mL of the buffersolution. The particle dispersion should have a silica concentration ofabout 30 wt %. If the selected particle dispersion has a higher wt %,dilute the dispersion to 30 wt %. Stir the solution for ten minutes. Thefresh viscosity measurement was made at about this time.

Each sample is then allowed to sit at about room temperature until thenext viscosity measurement is made. As shown in Table 1, there waslittle, if any, change in viscosity for test samples prepared from theparticles of Examples 1-10 at 96 hours. In comparison, ComparativeExamples 1-4 are observed to thicken or gel over 96 hours. Because thesesamples had gelled at 96 hours, the final viscosity measurement was madeafter 84 hours, Table 2.

2. Preparation of the Metal Substrates.

Panels of cold-rolled steel and electrogalvanized steel used to test thecorrosion resistance of the cured coatings are pretreated as follows.The panels are treated with Parco Cleaner 1523, which is an alkalinecleaner available from Henkel Surface Technologies. The panels aresprayed with the cleaner (about 2% in water) at 120 ° F for 2 minutes.The cleaned panels are rinsed with a warm tap water spray for 30seconds. A coating composition of the invention is sprayed on the rinsedpanels for 30 seconds at ambient temperature. Alternatively, the panelsare immersed in the coating compositions. The coated panels are thenoptionally rinsed with a cold water spray rinse for 30 seconds.Typically, if a relatively high particle content coating composition ofthe invention is used a water rinse will follow to remove residual(unbound) particles from the panels. The water rinse is not usuallynecessary for relatively low particle content coating compositions. Thepanels are then dried at 300° F. for 5 minutes. Coating weight of thisinvention was obtained by measuring the metal content, e.g., silicon,titanium, and zirconium, using x-ray fluorescence of the coated panels.Silica coating weight can also be measured by theweigh-coat-weigh-strip-weigh procedure, where the invention is strippedby 45% potassium hydroxide at 170° F. TABLE 1 Acid stable viscosity(fresh) viscosity (96 hrs) Δ, change in Ex. particle sec. sec. viscosity1 Ludox TMA 14 15 1 2 Ludox AM 14 14 0 3 Ludox SK 14 14 0 4 Ludox SK-G14 14 0 5 Snowtex C 14 15 1 6 Snowtex O 14 14 0 7 Snowtex N 14 15 1 8ACC 800 14 14 0 9 Haloflex 202 15 15 0 10 ACC 901 15 15 0

TABLE 2 viscosity viscosity Comp. Non-acid stable (fresh) (84 hrs) Δ,change in after Ex. particle sec. sec. viscosity 96 hr 1 Cabospere A-20514 30 16 gel 2 Luodx AS-30 15 96 81 gel 3 Snowtex 40 14 112 98 gel 4Snowtex OUP 14 65 51 gel

3. Application of Finish Coat on Coated Substrates.

The coated and dried panels are painted with Duracron 200, a polyacrylicenamel coating commercially available from PPG Industries, Inc., orSunburst Yellow, an epoxy-polyester hybrid powder paint commerciallyavailable from Morton International. The painted panels are allowed tocure according to recommendations by the manufacturer.

4. Corrosion Tests.

To test the corrosion resistance of the panels, the panels are scribedand a salt solution (5% NaCl) is sprayed on the scribed panels foreither 500 hr or 750 hr (ASTM B-117 method). The corrosion resistance ofthe coated panels is evaluated by measuring the creepage from thescribe. The data reported in Table 3 is the distance in mm of thewidened scribe following corrosion by the spray solution on CRS panels.As a result, the smaller the number the more effective the corrosionresistance of the coating.

EXAMPLE 1

Fluorotitanic acid (0.4 g, 60%) and fluorozirconic acid (0.4 g, 20%) areadded to stirred distilled water (3989.2 g). As this mixture is stirred,10 g of Ludox® TMA (33% silica) is added. The pH of this mixture isadjusted to about 4 by adding ammonium carbonate and/or small amounts ofadditional fluorotitanic acid. The mixture is stirred for about twohours.

EXAMPLES 2 TO 10

Examples 2 to 10 are coating compositions prepared according to theprocedure of Example 1 with the exception of the type and theconcentration of acid-stable particle used. The type and weight percentof particles for Examples 1 to 10 is provided in Table 4. The weightpercent of fluorotitanic acid and fluorozirconic acid in Examples 2 to10 is about 0.01%. TABLE 3 Scribe creep Scribe creep Coating weightCoating (mm)^(a) (mm)^(b) mg/sq ft Bonderite 1090 with 4.2 4.2 60 PLN99A seal Example 1 3.6 4.2 15 Example 10 2.2 2.9 16^(a)500 hour salt spray, paint is Duracron 200.^(b)750 hour salt spray, paint is Sunburst Yellow.Bonderite B-1090 and PLN 99A are iron phosphate and polymer rinse fromHenkel Corp.

TABLE 4 Coating Coating Particle type Pass Acid thickness^(a) ParticleSurface weight Ex. and wt% Stability Test (nm) size^(b) (nm) modifiedmg/sq ft 1 0.25% Ludox ® TMA Yes 73 60 aluminum 15 2 0.25% Ludox ® AMYes 44 35 aluminum 9 3 0.25% Ludox ® SK Yes 44 35 aluminum 9 4 0.25%Ludox ® SK-G Yes 97 30 aluminum 20 5 1% Snowtex ® C Yes 44 31 aluminum 96 1% Snowtex ® O Yes 55 33 Proprietary 10.5 7 1% Snowtex ® N Yes 97 35Proprietary 20 8 0.5% ACC 800 Yes 103 95 n/a 11.5 9 0.5% Haloflex 202Yes 155 201 n/a 17.3 10 2% ACC 901 Yes 143 177 n/a 16 ^(a) A density of2.2 for silica particle and 1.2 for organic polymeric particles was usedwith the measured coating weight to obtain film thickness values. Silicaparticles are stripped with 45% KOH at 170 ° F. Polymeric particles weredried at 120 ° F and then acetone stripped. For Example #1, the coatingthickness was estimated from the following calculation with silicacoating weight of 15 mg/sqft and density of2.2 g/cubic centimeter:${\frac{15{\frac{mg}{sqft} \cdot \frac{g}{1000{mg}} \cdot \frac{sqft}{0.093{sqmeter}} \cdot \frac{sqmeter}{10000{sqcentimeter}}}}{2.2\frac{g}{{cubic} \cdot {centimeter}}} \approx {{73 \times 10^{- 7}}{centimeter}}} = {73{nm}}$

EXAMPLES 11 TO 16

Examples 11 to 16 are coating compositions prepared according to theprocedure of Example 1 with the exception of the concentration ofacid-stable particle, titanium and zirconium used. The weight percentsof particles, titanium, and zirconium for Examples 11 to 16 are providedin Table 5. The titanium and zirconium were provided in the form offluorotitanic and fluorozirconic acid. The titanium, zirconium andsilica contents were measured by inductively coupled plasma (ICP)spectroscopy.

EXAMPLES 17 TO 20

Examples 17 to 20 are coating compositions prepared according to theprocedure of Example 1 with the exception of the concentration ofacid-stable particle used, and the concentration of zirconium. Theweight percents of particles and zirconium for Examples 17 to 20 areprovided in Table 6. TABLE 5 Scribe creep (mm) CRS/ CRS/DuracronEG/Duracron Sunburst Coating 200, 500 hr 200, 20 cycles Yellow, 750 hrsweight Example silica % Ti % Zr % NSS GM9540P NSS mg/sq ft B-1090/ N/AN/A N/A 4.5 1.8 6 60 PLN99A 11 0.435 0.0144 0.0093 3.8 0.4 5.2 29.8 120.434 0.0098 0.0093 3.6 0.6 5.0 32 13 0.426 0.0088 0.009 4 0.8 5.8 26.614 0.439 0.0084 0.0088 3.9 0.6 5.6 20.6 15 0.425 0.0084 0.0088 4.4 0 5.017.1 16 0.409 0.0073 0.0084 4.2 0.2 5.8 16.7

COMPARATIVE EXAMPLES 1 TO 6

Comparative Examples 1 to 3 are coating compositions containingLudox®-type silica particles. Comparative Examples 4 and 5 are coatingcompositions containing Snowtex®-type silica particles. ComparativeExample.6 is a coating composition containing Cabosperse® A-205 silicaparticles.

Comparative Examples 1 to 6 are prepared according to the procedure ofExample 1 with the exception of the type of silica particles used. Theweight percent of fluorotitanic acid and fluorozirconic acid is about0.01%. Comparative Examples 1 to 6 do not contain acid-stable particles,and attempts to use these compositions failed to provide any coating tothe panels. Comparative Examples I to 6 are summarized with thecorresponding coating data in Table 7. TABLE 6 Scribe creep (mm)CRS/Duracron CRS/Sunburst CRS/Sunburst Coating CRS/Duracron 200, 20cycles Yellow, 750 hrs Yellow, 40 cycles weight, Example Silica % Zr %200, 500 hr NSS GM9540P NSS GP9540P mg/sq ft B-1090/ N/A N/A 3.9 3.2 7.67 57 PLN99A 17 0.0059 0.004 4.2 2.8 7.1 7.1 28.4 18 0.013 0.008 3.2 2.66.9 6.9 24.3 19 0.013 0.009 3.4 2.7 7.3 7.3 33.3 20 0.016 0.011 3.2 2.76.7 6.7 27.1

TABLE 7 Pass acid Particle Comparative Particle type stability Surfacesize Ex. No. and wt % test modified (nm) 1 0.25% Ludox ® AS-30 No no 122 0.25% Ludox ® HS No no 12 3 0.25% Ludox ® TM No no 20 4 Snowtex 40 Nono 15 5 Snowtex 50 No no 25 6 Cabosperse A-205 No no 150

1-40. (canceled)
 41. An article of manufacture comprising a metalsubstrate and a coating disposed on the metal substrate, wherein thecoating comprises a metal-oxide matrix comprising acid-stable particlesand one or more metals.
 42. The article according to claim 41, whereinthe metal substrate comprises two or more different metals.
 43. Thearticle according to claim 41, wherein the metal substrate comprises ametal selected from cold rolled steel, hot-rolled steel, stainlesssteel, steel coated with zinc metal, zinc alloys, electrogalvanizedsteel, Galvalume®, Galvanneal™, hot-dipped galvanized steel, aluminumalloys, aluminum plated steel substrates and combinations thereof. 44.The article according to claim 41, wherein the one or more metals of themetal-oxide matrix is selected from the group consisting of titanium,zirconium and silicon.
 45. The article according to claim 41, whereinthe acid-stable particles comprise one or more selected from the groupconsisting of aluminum-modified particles, nonaluminum-modifiedparticles, organic polymeric particles and combinations thereof.
 46. Thearticle according to claim 41, wherein the article has a coatingcoverage of the metal substrate of 5 mg/sq ft to 50 mg/sq ft.
 47. Thearticle according to claim 41, wherein the acid-stable particles arepresent in the coating at a concentration of S mg/sq ft to 25 mg/sq ft.48. The article according to claim 41, wherein the metal in the coatingis present at a concentration of 0.5 mg/sq ft to 6 mg/sq ft.
 49. Thearticle according to claim 41, wherein the acid-stable particles arepresent in the coating at a concentration of 10 mg/sq ft to 20 mg/sq ft.50. The article according to claim 41, wherein the coating has athickness of 75% to 125% of an average particle diameter of theacid-stable particles.
 51. The article according to claim 41, furthercomprising an additional coating.
 52. The article according to claim 51,wherein the additional coating is a paint applied to the coatingdisposed on the metal substrate.
 53. The article according to claim 52,wherein the paint is selected from a primer paint composition or a finalpaint coating.
 54. The article according to claim 52, wherein the paintis an acrylic or polyester paint.
 55. The article according to claim 52,wherein the paint is a powder paint.
 56. The article according to claim52, wherein the paint is an electrodeposited paint.
 57. The articleaccording to claim 51, wherein the additional coating comprises a metalphosphate coating disposed between the metal substrate and themetal-oxide matrix.
 58. The article according to claim 57, wherein themetal phosphate coating comprises an iron or zinc phosphate coating. 59.The article according to claim 41, wherein the acid-stable particlescomprise aluminum-modified silica particles, and the acid-stableparticles are present in the metal-oxide matrix in an amount of 0.005%to 5% by weight.
 60. The article according to claim 41, wherein theacid-stable particles comprise aluminum-modified silica particles, andthe acid-stable particles are present in the metal-oxide matrix in anamount of 0.006% to 1% by weight.
 61. The article according to claim 41,wherein the acid-stable particles comprise nonaluminum-modified silicaparticles, and the acid-stable particles are present in the metal-oxidematrix in an amount of 0.005% to 5% by weight.
 62. The article accordingto claim 41, wherein the metal-oxide matrix further comprises a reactionproduct of the acid-stable particles and one or more fluoroacids.
 63. Amethod comprising: contacting a metal substrate with a coatingcomposition comprising an aqueous mixture comprising: (i) 0.005% to 8%by weight on a dry weight basis of acid-stable particles, and (ii) oneor more fluoroacids, to form a corrosion resistant coating; and applyingan additional coating.
 64. The method according to claim 63, wherein theadditional coating is applied prior to contacting the substrate with thecoating composition.